Solid carrier component including a liquid polyorganosiloxane and methods for preparation and use of the solid carrier component

ABSTRACT

A solid carrier component includes a liquid polydiorganosiloxane, an ethylene-based polymer, and a maleated ethylene-based polymer. The solid carrier component is useful in processes for preparing filled composite articles, such as wood plastic composite building materials.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/883,679 filed 7 Aug. 2019 under 35 U.S.C. § 119 (e).U.S. Provisional Patent Application No. 62/883,679 is herebyincorporated by reference.

TECHNICAL FIELD

A solid carrier component includes a liquid polyorganosiloxane, anethylene-based polymer, and a maleated ethylene-based polymer. The solidcarrier component is formulated to minimize migration of the liquidpolyorganosiloxane out of the solid carrier component upon aging.

BACKGROUND

Using silicone fluids such as polydimethylsiloxanes as additives inthermoplastic polymer systems presented challenges in handling for theend use application. These silicone fluids are generally liquids andgums that are difficult to handle in producing products by processessuch as injection molding, profile extrusion or film manufacturing.These types of processes generally are not set up for feeding liquid orgum. The common solution to the problem is to produce a siliconemasterbatch by mixing a silicone fluid into a polymer pellet that can beblended as a solid into a final formulation during the finished goodmanufacturing.

Previous silicone masterbatches used silicone fluids of viscositiesgreater than 50,000 cSt so that the large molecular weight could preventthe material from migrating out of the pellet in manufacturing orhandling.

Problems to be Solved

Recent studies have shown that using a lower molecular weight, lowerviscosity silicone fluid (as compared to the silicone fluids ofviscosities greater than 50,000 cSt described above) can provideadditional benefits in extrusion processes, such as reducing shearrelated defects in extruded profiles, reducing torque, reducing melttemperature and/or reducing energy requirements to produce extrudedproducts, and/or and improving mixing in the extruder, thereby improvingfinal formulation costs and/or properties. These lower molecular weightsilicone fluids have been found to offer benefits superior to the highermolecular weight silicone fluids. However, these lower viscosity/lowmolecular weight silicone fluids can reintroduce the problems of pelletmanufacturing and “bleeding” of silicone in storage or handling thatlead to the high molecular weight solutions described above.

SUMMARY

A solid carrier component comprises an ethylene-based polymer, amaleated ethylene-based polymer, and a hydroxyl-functionalpolyorganosiloxane. The solid carrier component is useful forfabrication of wood plastic composite articles.

DETAILED DESCRIPTION

A solid carrier component comprises: 40% to 80% of (A) an ethylene-basedpolymer with a melt index>2 g/10 min measured at 190° C. and 2.16 Kgaccording to ASTM D1238—13, 10% to 25% of (B) a maleated ethylene-basedpolymer, 10% to 25% of (C) a bis-hydroxyl terminatedpolydiorganosiloxane with a viscosity of 5,000 mPa·s to 25,000 mPa·s;and 0 to 10% of (D) a filler. Alternatively, the solid carrier componentconsists essentially of starting materials (A), (B), (C), and (D).Alternatively, the solid carrier component consists of startingmaterials (A), (B), (C), and (D). Alternatively, the solid carriercomponent consists essentially of starting materials (A), (B), and (C).Alternatively, the solid carrier component consists of startingmaterials (A), (B), and (C).

(A) Ethylene-Based Polymer

The solid carrier component described above comprises (A) anethylene-based polymer. As used herein, “ethylene-based” polymers arepolymers prepared from ethylene monomers as the primary (i.e., greaterthan 50%) monomer component, though other co-monomers may also beemployed. “Polymer” means a macromolecular compound prepared by reacting(i.e., polymerizing) monomers of the same or different type, andincludes homopolymers and interpolymers. “Interpolymer” means a polymerprepared by the polymerization of at least two different monomer types.The generic term interpolymer includes copolymers (usually employed torefer to polymers prepared from two different monomer types), andpolymers prepared from more than two different monomer types (e.g.,terpolymers (three different monomer types) and tetrapolymers (fourdifferent monomer types)).

The ethylene-based polymer can be an ethylene homopolymer. As usedherein, “homopolymer” denotes a polymer comprising repeating unitsderived from a single monomer type, but does not exclude residualamounts of other components used in preparing the homopolymer, such ascatalysts, initiators, solvents, and chain transfer agents.

Alternatively, the ethylene-based polymer can be anethylene/alpha-olefin (“α-olefin”) interpolymer having an α-olefincontent of at least 1%, alternatively at least 5%, alternatively atleast 10%, alternatively at least 15%, alternatively at least 20%, oralternatively at least 25 wt % based on the entire interpolymer weight.These interpolymers can have an α-olefin content of less than 50%,alternatively less than 45%, alternatively less than 40%, oralternatively less than 35% based on the entire interpolymer weight.When an α-olefin is employed, the α-olefin can have 3 to 20 carbon atoms(C3-C20) and be a linear, branched or cyclic α-olefin. Examples of C3-20α-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and1-octadecene. The α-olefins can also have a cyclic structure such ascyclohexane or cyclopentane, resulting in an α-olefin such as3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane.Illustrative ethylene/α-olefin interpolymers include ethylene/propylene,ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene,ethylene/propylene/1-octene, ethylene/propylene/1-butene, andethylene/1-butene/1-octene.

The ethylene-based polymer can be one ethylene-based polymer or acombination of two or more ethylene-based polymers (e.g., a blend of twoor more ethylene-based polymers that differ from one another by monomercomposition, monomer content, catalytic method of preparation, molecularweight, molecular weight distributions, and/or densities). If a blend ofethylene-based polymers is employed, the polymers can be blended by anyin-reactor or post-reactor process.

The ethylene-based polymer can be a linear-low-density polyethylene(“LLDPE”). LLDPEs are generally ethylene-based polymers having aheterogeneous distribution of comonomer (e.g., α-olefin monomer), andare characterized by short-chain branching. For example, LLDPEs can becopolymers of ethylene and α-olefin monomers, such as those describedabove. LLDPEs may have densities ranging from 0.91 g/cm³ to 0.94 g/cm³.Densities for the LLDPEs and other ethylene-based polymers describedherein are determined by ASTM D792—13. LLDPEs suitable for use hereincan have a melt index (I₂)>2 g/10 min, alternatively 2.3 g/10 min to 20g/10 min, alternatively 2.3 g/10 min to 12 g/10 min, alternatively 2.3g/10 min to 6 g/10 min. Melt indices for LLDPEs and other ethylene-basedpolymers are determined at 190° C. and 2.16 Kg according to ASTMD1238—13. The LLDPE can have a melting temperature of at least 124° C.,alternatively 124° C. to 135° C., and alternatively 124° C. to 132° C.Melting temperatures for LLDPEs and other polyethylene-based polymersare determined by DSC.

LLDPE's are known in the art and may be produced by known methods. Forexample, LLDPE may be made using Ziegler-Natta catalyst systems as wellas single-site catalysts such as bis-metallocenes (sometimes referred toas “m-LLDPE”), post-metallocene catalysts, and constrained geometrycatalysts. LLDPEs include linear, substantially linear or heterogeneouspolyethylene copolymers or homopolymers. LLDPEs may contain less longchain branching than LDPEs, and LLDPEs include: substantially linearethylene polymers which are further defined in U.S. Pat. Nos. 5,272,236,5,278,272, and 5,582,923; homogeneously branched linear ethylene polymercompositions such as those in U.S. Pat. No. 3,645,992; and/orheterogeneously branched ethylene polymers such as those preparedaccording to the process disclosed in U.S. Pat. No. 4,076,698. TheLLDPEs can be made via gas-phase, solution-phase or slurrypolymerization or any combination thereof, using any type of reactor orreactor configuration known in the art.

Alternatively, the ethylene-based polymer can be a medium-densitypolyethylene (“MDPE”). MDPEs are ethylene-based polymers havingdensities generally ranging from 0.926 to 0.940 g/cm³. Alternatively,the MDPE can have a density ranging from 0.930 to 0.939 g/cm³. The MDPEcan have I₂>2 g/10 min, alternatively 2.3 g/10 min to 20 g/10 min,alternatively 2.3 g/10 min to 12 g/10 min, and alternatively 2.3 g/10min to 6 g/10 min. The MDPE can have a melting temperature of at least124° C., alternatively 124° C. to 135° C., and alternatively 124° C. to132° C. MDPE may be made using chromium or Ziegler-Natta catalysts orusing metallocene, constrained geometry, or single site catalysts, andtypically have MWD greater than 2.5.

Alternatively, the ethylene-based polymer can be a high-densitypolyethylene (“HDPE”). HDPEs are ethylene-based polymers havingdensities of at least 0.940 g/cm³. Alternatively, the HDPE can have adensity of >0.940 g/cm³ to 0.970 g/cm³, alternatively >0.940 g/cm³ to0.965 g/cm³, alternatively >0.940 to 0.952 g/cm³. The HDPE can have amelting temperature of at least 124° C., alternatively 124° C. to 135°C., alternatively 124° C. to 132° C., alternatively 130° C. to 133° C.,and alternatively 131° C. to 132° C. The HDPE can have a melt index(I₂) >2 g/10 min, alternatively 2.3 g/10 min to 20 g/10 min,alternatively 3 g/10 min to 12 g/10 min, alternatively 4 g/10 min to 7g/10 min. The HDPE can have a polydispersity index (“PDI”) of 1.0 to30.0, alternatively 2.0 to 15.0, as determined by GPC.

The HDPE suitable for use herein can be unimodal. As used herein,“unimodal” denotes an HDPE having a MWD such that its GPC curve exhibitsonly a single peak with no discernible second peak, or even a shoulderor hump, relative to such single peak. In contrast, “bi-modal” meansthat the MWD in a GPC curve exhibits the presence of two componentpolymers, such as by having two peaks or where one component may beindicated by a hump, shoulder, or tail relative to the peak of the othercomponent polymer. HDPEs are known in the art and may be made by knownmethods. For example, HDPEs may be prepared with Ziegler-Nattacatalysts, chrome catalysts or even metallocene catalysts.

Alternatively, the ethylene-based polymer for starting material (A) maybe selected from the group consisting of HDPE, MDPE, LLDPE, and acombination thereof. Alternatively, the ethylene-based polymer forstarting material (A) may be selected from the group consisting of HDPE,LLDPE, and a combination thereof. Alternatively, the ethylene-basedpolymer for starting material (A) may be selected from the groupconsisting of HDPE and LLDPE. Alternatively, the ethylene-based polymerfor starting material (A) may be HDPE. Preparation methods forethylene-based polymers are well known in the art. Any methods known orhereafter discovered for preparing an ethylene-based polymer having thedesired properties may be employed for making the ethylene-basedpolymer. Suitable LLDPEs, MDPEs, and HDPEs may be prepared by methodsdescribed above or those disclosed in PCT Publication No. WO2018/049555and U.S. Patent Application Publication No. 2019/0023895, and thereferences cited therein. Suitable ethylene-based polymers for useherein are commercially available from The Dow Chemical Company ofMidland, Mich., USA, and are exemplified by those with melt index>2 g/10min shown below in Table 2.

The ethylene-based polymer can be present in the solid carrier componentin an amount of 40% to 80%, alternatively 50% to 80%, alternatively 50%to 70%, alternatively 50% to 60%, and alternatively 60% to 70% based oncombined weights of all starting materials in the solid carriercomponent.

(B) Maleated Ethylene-Based Polymer

The solid carrier component described above further comprises (B) amaleated ethylene-based polymer. As used herein, the term “maleated”indicates a polymer (e.g., an ethylene-based polymer) that has beenmodified to incorporate a maleic anhydride monomer. Maleic anhydride canbe incorporated into the ethylene-based polymer by any methods known orhereafter discovered in the art. For instance, the maleic anhydride canbe copolymerized with ethylene and other monomers (if present) toprepare an interpolymer having maleic anhydride residues incorporatedinto the polymer backbone. Alternatively, the maleic anhydride can begraft-polymerized to the ethylene-based polymer. Techniques forcopolymerizing and graft polymerizing are known in the art.

The maleated ethylene-based polymer may be an ethylene-based polymerhaving maleic anhydride grafted thereon. The ethylene-based polymerprior to being maleated can be any of the ethylene-based polymersdescribed above, alternatively, the ethylene-based polymer used formaleating may have a melt index lower than that melt index of theethylene-based polymer described above. The starting ethylene-basedpolymer can be selected from a linear-low density polyethylene, amedium-density polyethylene, and a high-density polyethylene.Alternatively, the starting ethylene-based polymer can be a high-densitypolyethylene.

The maleated ethylene-based polymer may have a density of at least 0.923g/cm³. Alternatively, the maleated ethylene-based polymer can have adensity of 0.923 g/cm³ to 0.962 g/cm³, alternatively 0.940 g/cm³ to0.962 g/cm³, and alternatively 0.923 g/cm³ to 0.940 g/cm³. The maleatedethylene-based polymer may have a melt index (I₂) of 0.1 g/10 min to 25g/10 min, alternatively 1 g/10 min to 2 g/10 min, alternatively 2 g/10min to 25 g/10 min, alternatively 2 g/10 min to 12 g/10 min,alternatively 3 g/10 min to 25 g/10 min, and alternatively 3 g/10 min to12 g/10 min. Densities, melt indices, and melting temperatures of themaleated ethylene-based polymers may be evaluated using the ASTM methodsdescribed herein for the ethylene-based polymers. The maleatedethylene-based polymer can have a maleic anhydride content of at least0.25%, alternatively an amount of 0.25% to 2.5%, and alternatively 0.5%to 1.5%, each based on the total weight of the maleated ethylene-basedpolymer. Maleic anhydride concentrations may be determined by atitration method, which takes dried resin and titrates with 0.02N KOH todetermine the amount of maleic anhydride. The dried polymers aretitrated by dissolving 0.3 to 0.5 grams of maleated ethylene-basedpolymer in 150 mL of refluxing xylene. Upon complete dissolution,deionized water (four drops) is added to the solution and the solutionis refluxed for 1 hour. Next, 1% thymol blue (a few drops) is added tothe solution and the solution is over titrated with 0.02N KOH in ethanolas indicated by the formation of a purple color. The solution is thenback-titrated to a yellow endpoint with 0.05N HCl in isopropanol.

Suitable maleated ethylene-based polymers for starting material (B) maybe prepared by known methods, such as those disclosed in PCT PublicationNo. WO2018/049555 and the references cited therein. Alternatively,maleated ethylene-based polymers may be prepared by a process forgrafting maleic anhydride on an ethylene-based polymer, which can beinitiated by decomposing initiators to form free radicals, includingazo-containing compounds, carboxylic peroxyacids and peroxyesters, alkylhydroperoxides, and dialkyl and diacyl peroxides, among others. Many ofthese compounds and their properties have been described (Reference: J.Branderup, E. Immergut, E. Grulke, eds. “Polymer Handbook,” 4th ed.,Wiley, New York, 1999, Section 11, pp. 1-76.). Alternatively, thespecies that is formed by the decomposition of the initiator may be anoxygen-based free radical. Alternatively, the initiator may be selectedfrom the group consisting of carboxylic peroxyesters, peroxyketals,dialkyl peroxides, and diacyl peroxides. Exemplary initiators, commonlyused to modify the structure of polymers, are listed in U.S. Pat. No.7,897,689, in the table spanning Col. 48 line 13-Col. 49 line 29.Alternatively, the grafting process for making maleated ethylene-basedpolymers can be initiated by free radicals generated by thermaloxidative processes. Suitable maleated ethylene-based polymers arecommercially available from The Dow Chemical Company, of Midland, Mich.,USA, and examples are shown below in Table 1.

TABLE 1 Examples of Maleated Ethylene-Based Polymers a random ethylenehigh density copolymer incorporating polyethylene a monomer which isgrafted with very classified as being high maleic a maleic anhydrideanhydride copolymer Type equivalent graft level Density (g/cm³) 0.9400.962 I₂ (g/10 min) 25 2.0 Melting Temperature 108 130 (° C.)

In Table 1, melting temperature of the random ethylene copolymerincorporating a monomer which is classified as being a maleic anhydrideequivalent was measured by DSC according to ASTM D3418—15, and meltingtemperature of the high density polyethylene grafted with very highmaleic anhydride copolymer graft level was measured by DSC wherein afilm was conditioned at 230° C. for 3 minutes before cooling at a rateof 10° C. per minute to a temperature of −40° C. After the film was keptat −40° C. for 3 minutes, the film was heated to 200° C. at a rate of10° C. per minute.

The maleated ethylene-based polymer can be present in the solid carriercomponent in an amount of 10% to 25%, alternatively 10% to <25%,alternatively >10% to <20%, alternatively 10% to 15%, alternatively 15%to 20%, and alternatively 10% to 20%, based on combined weights of allstarting materials in the solid carrier component.

(C) Bis-Hydroxyl-Terminated Polydiorganosiloxane

The solid carrier component further comprises (C) abis-hydroxyl-terminated polydiorganosiloxane with a viscosity of 5,000mPa·s to 25,000 mPa·s. Viscosity was measured at 25° C. at 5 RPM on aBrookfield DV-III cone & plate viscometer with #CP-52 spindle. Thebis-hydroxyl-terminated polydiorganosiloxane may have formula:

where each R is an independently selected monovalent hydrocarbon groupof 1 to 18 carbon atoms, and subscript x has a value sufficient to givethe bis-hydroxyl-terminated polydiorganosiloxane the viscosity describedabove. Alternatively, viscosity may be 5,000 mPa·s to 20,000 mPa·s,alternatively 5,000 mPa·s to 15,000 mPa·s, alternatively 6,000 mPa·s to13,500 mPa·s, alternatively 12,000 mPa·s to 15,000 mPa·s, alternatively5,400 mPa·s to 6,600 mPa·s, and alternatively 5,400 mPa·s to 15,000mPa·s; and the value for subscript x is sufficient to give thebis-hydroxyl-terminated polydiorganosiloxane this viscosity.

Alternatively, each R may be an alkyl group of 1 to 18 carbon atoms,alternatively 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms,and alternatively 1 to 4 carbon atoms, and starting material (C) may bea bis-hydroxyl-terminated polydialkylsiloxane. Suitable alkyl groupsinclude methyl, ethyl, propyl (including n-propyl and iso-propyl), andbutyl (including n-butyl, tert-butyl, sec-butyl, and iso-butyl).Alternatively, each R may be methyl.

Suitable bis-hydroxy-terminated polydiorganosiloxanes may be prepared bymethods known in the art such as hydrolysis and condensation ofappropriate organohalosilane monomers and/or equilibration of linear andcyclic polyorganosiloxanes. The bis-hydroxy-terminatedpolydiorganosiloxane may be a bis-OH terminated polydimethylsiloxane,which is commercially available. Bis-OH terminated polydimethylsiloxanesare commercially available from Dow Silicones Corporation of Midland,Mich., USA

The hydroxyl-terminated polydiorganosiloxane may be present in the solidcarrier component in an amount of 10% to 25%, alternatively 10% to <25%,alternatively >10% to <25%, alternatively 10% to 20%, andalternatively >10% to 20%, based on combined weights of all startingmaterials in the solid carrier component.

(D) Filler

The solid carrier component may optionally further comprise up to 10% ofa filler. The filler may be a mineral filler. Specific examples ofsuitable fillers include, but are not limited to, calcium carbonate,silica, quartz, fused quartz, talc, mica, clay, kaolin, wollastonite,feldspar, aluminum hydroxide, carbon black, and graphite. Fillers areknown in the art and are commercially available, e.g., ground silica issold under the name MIN-U-SIL by U.S. Silica of Berkeley Springs, W.Va., USA. Suitable precipitated calcium carbonates include Winnofil™ SPMfrom Solvay and Ultra-pflex™ and Ultra-pflex™ 100 from SpecialtyMinerals, Inc. of Quinnesec, Mich., USA.

The shape and dimensions of the filler is not specifically restricted.For example, the filler may be spherical, rectangular, ovoid, irregular,and may be in the form of, for example, a powder, a flour, a fiber, aflake, a chip, a shaving, a strand, a scrim, a wafer, a wool, a straw, aparticle, and combinations thereof. Dimensions and shape are typicallyselected based on the type of the filler utilized, the selection ofother starting materials included within the solid carrier component.

Regardless of the selection of the filler, the filler may be untreated,pretreated, or added in conjunction with an optional filler treatingagent, described below, which when so added may treat the filler in situor prior to incorporation of the filler in the solid carrier component.Alternatively, the filler may be surface treated to facilitate wettingor dispersion in the solid carrier component, which when so added maytreat the filler in situ in the composition.

The filler treating agent may comprise a silane such as an alkoxysilane,an alkoxy-functional oligosiloxane, a cyclic polyorganosiloxane, ahydroxyl-functional oligosiloxane such as a dimethyl siloxane or methylphenyl siloxane, an organosilicon compound, a stearate, or a fatty acid.The filler treating agent may comprise a single filler treating agent,or a combination of two or more filler treating agents selected fromsimilar or different types of molecules.

The filler treating agent may comprise an alkoxysilane, which may be amono-alkoxysilane, a di-alkoxysilane, a tri-alkoxysilane, or atetra-alkoxysilane. Alkoxysilane filler treating agents are exemplifiedby hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane,dodecyltrimethoxysilane, tetradecyltrimethoxysilane,phenyltrimethoxysilane, phenylethyltrimethoxysilane,octadecyltrimethoxysilane, octadecyltriethoxysilane, and a combinationthereof. In certain aspects the alkoxysilane(s) may be used incombination with silazanes, which catalyze the less reactivealkoxysilane reaction with surface hydroxyls. Such reactions aretypically performed above 100° C. with high shear with the removal ofvolatile by-products such as ammonia, methanol and water.

Suitable filler treating agents also include alkoxysilyl functionalalkylmethyl polysiloxanes, or similar materials where the hydrolyzablegroup may comprise, for example, silazane, acyloxy or oximo.

Alkoxy-functional oligosiloxanes can also be used as filler treatingagents. Alkoxy-functional oligosiloxanes and methods for theirpreparation are generally known in the art. Other filler treating agentsinclude mono-endcapped alkoxy functional polydiorganosiloxanes, i.e.,polyorganosiloxanes having alkoxy functionality at one end.

Alternatively, the filler treating agent can be any of the organosiliconcompounds typically used to treat silica fillers. Examples oforganosilicon compounds include organochlorosilanes such asmethyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane; organosiloxanes such as hydroxy-endblockeddimethylsiloxane oligomer, silicon hydride functional siloxanes,hexamethyldisiloxane, and tetramethyldivinyldisiloxane; organosilazanessuch as hexamethyldisilazane and hexamethylcyclotrisilazane; andorganoalkoxysilanes such as alkylalkoxysilanes with methyl, propyl,n-butyl, i-butyl, n-hexyl, n-octyl, i-octyl, n-decyl, dodecyl,tetradecyl, hexadecyl, or octadecyl substituents. Organoreactivealkoxysilanes can include amino, methacryloxy, vinyl, glycidoxy,epoxycyclohexyl, isocyanurato, isocyanato, mercapto, sulfido,vinyl-benzyl-amino, benzyl-amino, or phenyl-amino substituents.Alternatively, the filler treating agent may comprise anorganopolysiloxane. Alternatively, certain filler treating agents, suchas chlorosilanes, may be hydrolyzed at the filler surface.Alternatively, the filler treating agent may take advantage of multiplehydrogen bonds, either clustered or dispersed or both, as the method tobond the organosiloxane to the surface of the filler. The organosiloxanecapable of hydrogen bonding has an average, per molecule, of at leastone silicon-bonded group capable of hydrogen bonding. The group may beselected from: a monovalent organic group having multiple hydroxylfunctionalities or a monovalent organic group having at least one aminofunctional group. Hydrogen bonding may be a primary mode of bonding ofthe organosiloxane to the filler. The organosiloxane may be incapable offorming covalent bonds with the filler. The organosiloxane capable ofhydrogen bonding may be selected from the group consisting of asaccharide-siloxane polymer, an amino-functional organosiloxane, and acombination thereof. Alternatively, the polyorganosiloxane capable ofhydrogen bonding may be a saccharide-siloxane polymer.

Alternatively, the filler treating agent may comprise alkylthiols suchas octadecyl mercaptan and others, and fatty acids such as oleic acid,stearic acid, titanates, titanate coupling agents, zirconate couplingagents, and a combination thereof. One skilled in the art could optimizea filler treating agent to aid dispersion of the filler without undueexperimentation.

The filler may be a single filler or a combination of two or morefillers that differ in at least one property such as type of filler,method of preparation, treatment or surface chemistry, fillercomposition, filler shape, filler surface area, average particle size,and/or particle size distribution. A filler may be included in the solidcarrier component in an amount of 0 to 10%, alternatively >0 to 10%based on combined weights of all starting materials in the solid carriercomponent.

Method of Making the Solid Carrier Component

The solid carrier component is a solid at ambient temperature andpressure (e.g. 25° C. and 1 atmosphere). The solid carrier component maybe formed by combining the starting materials in any order. The solidcarrier component may be prepared by forming a mixed composition from(A) the ethylene-based polymer, (B) the maleated ethylene-based polymer,(C) the bis-hydroxyl-terminated polydiorganosiloxane, and when present(D), the filler, by dispersing under mixing or shear, e.g., withsuitable mixing equipment. For example, the mixed composition may bedispersed in a vessel equipped with an agitator and/or mixing blades.The vessel may be, for example, an internal mixer, such as a Banbury,Sigma (Z) Blade, or Cavity Transfer style mixer. Alternatively or inaddition, the mixed composition may be dispersed in or processed by anextruder, which may be any extruder, e.g., a single screw extruder withrotational and/or reciprocating (co-kneader) screws, as well asmulti-screw devices comprising two or more screws, which may be alignedtangentially or partially/fully intermeshing, revolving in either a co-or counter-rotational direction. Alternatively, a conical extruder maybe used to disperse the mixed composition described herein.

The solid carrier components prepared as described above arere-processable and may be prepared for feeding in subsequent processes.The mixed composition prepared as described above may be, for example,substantially continuous ribbons or discontinuous pellets or particlesor powders. Substantially continuous ribbons can be formed bypressurizing the mixed composition and passing it through a die tocreate continuous strands or tapes that are subsequently cooled beforebeing suitably packaged. Alternatively, the strand or tape may becomminuted to form pellets or powders. The mixing device may alsoproduce the pressure and/or heat needed to process the mixed compositionthrough the die when the mixing device is an extruder, which may be anyextruder, e.g., BUSS kneader, or a single screw extruder with rotationaland/or reciprocating (co-kneader) screws, as well as multi-screw devicescomprising two or more screws, which may be aligned tangentially orpartially/fully intermeshing, revolving in either a co- orcounter-rotational direction. A conical extruder may be used for mixingand pressurizing the mixed composition. Alternately, a gear pump may beused to generate the pressure needed for extrusion after the mixedcomposition has been mixed. Discontinuous forms of the mixed compositionmay be created by chopping continuous ribbons of mixed composition intoshorter lengths. Alternatively, large pieces of mixed composition may bereduced to usable sizes by use of a grinder or shredder.

The solid carrier component may be formed by a method performedcontinuously or semi-continuously in an extruder, such as a twin screwextruder (in which the screws are concurrently rotated, partially orfully intermeshing, alternatively counter rotated aligned eithertangentially or partially or fully intermeshing). Alternatively, (C) thebis-hydroxyl-terminated polydiorganosiloxane may be disposed in theextruder concurrently with (A) the ethylene-based polymer and (B) themaleated ethylene-based polymer, (and optionally (D) the filler).Alternatively, (C) the bis-hydroxyl-terminated polydiorganosiloxane maybe disposed in the extruder after melting (A) the ethylene-based polymerand/or (B) the maleated ethylene-based polymer (and before adding (D)the filler, if any will be added to the mixed composition).Alternatively, (C) the bis-hydroxyl-terminated polydiorganosiloxane maybe disposed in the extruder after (D) the filler, when present, andbefore one or both of (A) the ethylene-based polymer and (B) themaleated ethylene-based polymer and before the mixed composition exitsthe extruder. Alternatively, (D) the filler may be disposed in theextruder concurrently with (C) the bis-hydroxyl-terminatedpolydiorganosiloxane, then (A) the ethylene-based polymer and (B) themaleated ethylene-based polymer may be disposed in the extruder to givea mixture and the temperature increased to a temperature suitable forcompounding the mixture. The extruder may have one or more zones, suchas 1 to 3, alternatively 1 to 12, alternatively 3 to 12, oralternatively 3 to 10 zones, where starting materials can be added. Thezones may be heated at different temperatures and incorporate variousfunctional stages including conveying, melting, mixing, deaeration,vacuum, pressurization, and forming.

Alternatively, (A) the ethylene-based polymer and (B) the maleatedethylene-based polymer may be disposed in a first zone of the extruder,which is heated at +/−30° C. within the melting temperature of (A) theethylene-based polymer and/or (B) the maleated ethylene-based polymer.Starting material (C), the bis-hydroxyl-terminated polydiorganosiloxane,may be disposed in a second zone of the extruder, which is heated at 10°C. to 90° C. above the melting temperature of (A) the ethylene-basedpolymer and/or (B) the maleated ethylene-based polymer. Startingmaterial (D), the filler, when present, may be disposed in one or moreof the first, second, or subsequent zones of the extruder.Alternatively, (D) the filler and (C) the bis-hydroxyl-terminatedpolydiorganosiloxane may be combined before adding the resultingcombination to the extruder. As noted above, the temperature utilized istypically less than a degradation temperature of the starting materialsof the solid carrier component. The mixture may be stripped to removeany air, moisture or byproducts prior to pressurization and forming inthe die of the extruder. The vacuum, pressurization, and forming zonesmay also be heated, and the temperatures utilized by the extruder,including the temperature of any zone and the die, does not exceed adegradation temperature of starting materials (A), (B), (C), and (D).The degradation temperature of starting materials (A), (B), (C), and (D)is contingent on the selection thereof, as understood by one of skill inthe art. The resulting extruded strand may be comminuted by anyconvenient means to form the solid carrier component.

The solid carrier component is typically in particulate form, and maybe, for example, in the form of particles, pellets, or powders. Anaverage particle size of the solid carrier component is a function ofdesired properties and end use thereof. The solid carrier component maybe a powder. Alternatively, the solid carrier component may be a pellet.Pellets typically have greater average particle sizes than powders.

Method of Use

The solid carrier component described above is useful in preparation offilled ethylene-based polymer composite articles, such as wood plasticcomposite (WPC) articles. The solid carrier component may be used in aWPC composition, which can be used in a method for preparing a WPCarticle. A method for preparing a WPC article comprises:

1) combining starting materials comprising

-   -   (a) a lignocellulosic-based filler,    -   (b) an ethylene-based polymer, and    -   (c) the solid carrier component described above, thereby        preparing a WPC composition; and        2) forming the WPC article from the WPC composition.

Starting Material (a) Lignocellulosic-Based Filer

The lignocellulosic-based filler comprises, alternatively consistsessentially of, alternatively consists of, a lignocellulosic material.Typically, the lignocellulosic-based filler consists of thelignocellulosic material. The lignocellulosic-based filler, as well asthe lignocellulosic material, may comprise any matter derived from anyplant source. When the lignocellulosic-based filler consists essentiallyof or consists of lignocellulosic material, the lignocellulosic materialmay also include some water or moisture content, although thelignocellulosic material, as well as the lignocellulosic-based filler,is typically dry, i.e., does not contain any free moisture content butfor that which may be associated with the relative humidity in anenvironment in which the lignocellulosic-based filler is prepared,derived, formed, and/or stored. The same is typically true for otherspecies of (a) the lignocellulosic-based filler, but is noted in regardsto lignocellulosic-based fillers as lignocellulosic materials generallyinclude some water content as harvested/prepared prior to any drying orend use.

The lignocellulosic-based filler typically comprises carbohydratepolymers (e.g. cellulose and/or hemicellulose), and may further comprisean aromatic polymer (e.g. lignin). The lignocellulosic-based filler istypically a natural lignocellulosic material, i.e., is not syntheticallyderived. For example, the lignocellulosic-based filler is typicallyderived from wood (hardwood, softwood, and/or plywood). Alternatively orin addition, the lignocellulosic-based filler may compriselignocellulosic material from other non-wood sources, such aslignocellulosic material from plants, or other plant-derived polymers,for example agricultural by-products, chaff, sisal, bagasse, wheatstraw, kapok, ramie, henequen, corn fiber or coir, nut shells, flax,jute, hemp, kenaf, rice hulls, abaca, peanut hull, bamboo, straw,lignin, starch, or cellulose and cellulose-containing products, andcombinations thereof.

Specific examples of suitable hardwoods from which thelignocellulosic-based filler may be derived include, but are not limitedto, ash, aspen, cottonwood, basswood, birch, beech, chestnut, gum, elmeucalyptus, maple, oak, poplar, sycamore, and combinations thereof.Specific examples of suitable softwoods from which thelignocellulosic-based filler may be derived include, but are not limitedto, spruce, fir, hemlock, tamarack, larch, pine, cypress, redwood, andcombinations thereof. Combinations of different hardwoods, combinationsof different softwoods, or combinations of hardwood(s) and softwood(s)may be utilized together as the lignocellulosic-based filler. Thelignocellulosic-based filler may be virgin, recycled, or a combinationthereof.

The lignocellulosic-based filler may have any form and size, e.g., fromnanometer to millimeter particle size. For example, thelignocellulosic-based filler may comprise a powder, a pulp, a flour,sawdust, a fiber, a flake, a chip, a shaving, a strand, a scrim, awafer, a wool, a straw, a particle, or any combination thereof. Thelignocellulosic-based filler may be formed via a variety of techniquesknown to one of skill in the art, typically as a function of the formthereof. For example, the lignocellulosic-based filler can be preparedby comminuting logs, branches, industrial wood residue, or roughpulpwood. The lignocellulosic-based filler may be comminuted to adesired particle size. For example, the lignocellulosic-based filler maybe comminuted with any convenient equipment, such as a hammer mill,which results in the lignocellulosic-based filler having a particle sizesuitable for use in mixing processes. The desired particle size istypically selected by one of skill in the art based on the particularmixing process utilized and desired properties of the polymer compositearticle. By particle size, it is meant the dimensions of thelignocellulosic-based filler, regardless of shape, and includes, forexample, dimensions associated with the lignocellulosic-based fillerwhen in the form of fibers. As known in the art, lignocellulosic-basedfillers may be pelletized, or otherwise in the form of pellets, whichmay substantially maintain shape and dimension when incorporated intothe composition or which may form smaller particles in the composition.

The shape and dimensions of the lignocellulosic-based filler is also notspecifically restricted. For example, the lignocellulosic-based fillermay be spherical, rectangular, ovoid, irregular, and may be in the formof, for example, a powder, a flour, a fiber, a flake, a chip, a shaving,a strand, a scrim, a wafer, a wool, a straw, a particle, andcombinations thereof. Dimensions and shape are typically selected basedon the type of the lignocellulosic-based filler utilized, the selectionof other starting materials included within the WPC composition, and theend use application of the WPC article formed therewith.

The lignocellulosic-based filler may present in the WPC composition inan amount of 10% to 89.5%, alternatively 20% to 75%, alternatively 30%to 70%, alternatively 45% to 65%, based on combined weights of allstarting materials in the WPC composition. Typically, it is desirable tomaximize the relative amount of (a) the lignocellulosic-based filler inthe WPC composition, which reduces overall cost thereof, so long asdesirable properties of the WPC article formed therewith are maintainedor obtained. One skilled in the art understands that the amount of (a)the lignocellulosic-based filler may be modified for this purpose,including a balance of cost and resulting properties, as well as thepresence or absence of other optional starting materials, as describedbelow.

Starting Material (b) Ethylene-Based Polymer

Starting material (b) in the WPC composition is an ethylene-basedpolymer. The ethylene-based polymer may be any of the ethylene-basedpolymers prepared by methods such as those disclosed in PCT PublicationNo. WO2018/049555 and U.S. Patent Application Publication No.2019/0023895, and the references cited therein. Alternatively, theethylene-based polymer may be an ethylene-based polymer as describedabove for starting material (A) in the solid carrier component.Alternatively, the ethylene-based polymer may be selected from HDPE,MDPE, Low Density Polyethylene (LDPE), LLDPE, Very Low DensityPolyethylene (VLDPE), Ultra Low Density Polyethylene (ULDPE), LowDensity Low Molecular Weight Polyethylene (LDLMWPE), or a combinationthereof. Examples of suitable ethylene-based polymers, which arecommercially available from The Dow Chemical Company of Midland, Mich.,USA are shown below in Table 2.

TABLE 2 Ethylene - Based Polymers Melting Temper- Density I₂ ature Type(g/cm³) (g/10 min) (° C.) high density polyethylene 0.950 12 132 narrowmolecular weight 0.952 6.8 131 distribution high density polyethylenehomopolymer high density polyethylene 0.952 4.4 131 high densitypolyethylene 0.952 10 130 high density polyethylene 0.954 20 130 highdensity polyethylene homopolymer 0.961 0.80 133 high densitypolyethylene homopolymer 0.965 8.3 133 with a narrow molecular weightdistribution ethylene/1-octene linear-low-density 0.917 2.3 123polyethylene copolymer ethylene/1-octene linear-low-density 0.919 6.0124 polyethylene copolymer polyethylene resin, which is a narrow 0.91725 124 molecular weight distribution copolymer

The ethylene-based polymer for use in the WPC composition may comprisevirgin polymer and/or recycled polymer. Without wishing to be bound bytheory, it is thought that the ethylene-based polymer may comprise 50%recycled polyethylene. The recycled ethylene-based polymer, if utilized,may be sourced from industrial production streams, as well as frompost-industrial and/or post-consumer sources. The selection of thespecific ethylene-based polymer, as well as any ratio of virgin polymerto recycled polymer, if utilized in concert, is typically a function ofcost and desired properties of the WPC article formed therewith. The WPCcomposition may contain 10% to 80% of (b) the ethylene-based polymer,based on combined weights of all starting materials in the WPCcomposition. The WPC composition may contain a sufficient amount of (i)the solid carrier component described above to give the WPC compositiona content of the bis-hydroxyl terminated polydiorganosiloxane of 0.5% to4%, alternatively 1% to 4%.

The WPC composition may optionally further comprise one or moreadditional starting materials. For example, one or more startingmaterials may be selected from the group consisting of (d) an additionalfiller which is distinct from the lignocellulosic filler of startingmaterial (a), (e) a colorant, (f) a blowing agent, (g) a UV stabilizer,(h) an antioxidant, (i) a process aid, (j) a preservative, (k) abiocide, (l) a flame retardant, and (m) an impact modifier. Eachadditional starting material, if utilized, may be present in the WPCcomposition in an amount of greater than 0 to 30% based on combinedweights of all starting materials in the WPC composition. The WPCcomposition may also include other optional additives, as known in theart. Such additives are described, for example, in Walker, Benjamin M.,and Charles P. Rader, eds. Handbook of thermoplastic elastomers. NewYork: Van Nostrand Reinhold, 1979; Murphy, John, ed. Additives forplastics handbook. Elsevier, 2001.

When selecting starting materials to include in the WPC composition,there may be overlap between types of starting materials because certainstarting materials described herein may have more than one function. Forexample, (d) the additional filler may be a filler described above forstarting material (D) in the solid carrier component. Certain of suchfillers may be useful as additional fillers and as colorants, and evenas flame retardants, e.g., carbon black. When selecting startingmaterials for the WPC composition, the starting materials selected foreach embodiment are distinct from one another.

The WPC composition may be formed under mixing or shear, e.g., withsuitable mixing equipment. For example, the WPC composition may beformed in a vessel equipped with an agitator and/or mixing blades. Thevessel may be, for example, an internal mixer, such as a Banbury, Sigma(Z) Blade, or Cavity Transfer style mixer. Alternatively or in addition,the WPC composition may be formed in or processed by an extruder, whichmay be any extruder, e.g. a single screw extruder with rotational and/orreciprocating (co-kneader) screws, as well as multi-screw devicescomprising two or more screws, which may be aligned tangentially orpartially/fully intermeshing, revolving in either a co- orcounter-rotational direction. Alternatively, a conical extruder may beused for forming the WPC composition described herein.

In the method for preparing the WPC article as described above, themethod also comprises forming the WPC article from the WPC composition.The WPC composition may be prepared, e.g., in the vessel, andsubsequently removed from the vessel to form the WPC article withseparate equipment. Alternatively, the same equipment may be utilized toprepare the WPC composition and subsequently form WPC article. Forexample, the WPC composition may be prepared and/or mixed in anextruder, and the extruder may be utilized to form the WPC article withthe WPC composition. Alternatively, the WPC article may be formed viamolding, e.g., with an injection or transfer molding process. The WPCcomposition may be formed independently and disposed in the mold onceformed.

The method described above comprises forming the WPC article from theWPC composition, which may comprise forming the WPC composition into adesired shape. The desired shape depends on end use applications of theWPC article. One of skill in the art understands how dies for extrusionand molds for molding may be selected and created based on the desiredshape of the WPC article.

The method may be performed continuously or semi-continuously in anextruder, such as a twin screw extruder (in which the screws areconcurrently rotated, partially or fully intermeshing, alternativelycounter rotated aligned either tangentially or partially or fullyintermeshing). The solid carrier component may be disposed in theextruder concurrently with (a) the lignocellulosic-based filler and (b)the ethylene-based polymer. Alternatively, the solid carrier componentmay be disposed in the extruder after melting (b) the ethylene-basedpolymer and before adding (a) the lignocellulosic-based filler.Alternatively, the solid carrier component may be disposed in theextruder after (a) the lignocellulosic-based filler and (b) theethylene-based polymer and before the WPC article exits the extruder.Alternatively, (a) the lignocellulosic-based filler may be disposed inthe extruder concurrently with the solid carrier component, where theyare heated to effect surface treatment of (a) the lignocellulosic-basedfiller with the hydroxyl-terminated polydiorganosiloxane in (c) thesolid carrier component, then (b) the ethylene-based polymer is disposedin the extruder to give a mixture and the temperature increased to atemperature suitable for compounding the mixture and forming the WPCarticle. The extruder may have one or more zones, such as 1 to 3, or 3to 8, or 1 to 12, zones, where starting materials can be added. Thezones may be heated at different temperatures.

Alternatively, (b) the ethylene-based polymer may be disposed in a firstzone of the extruder, which is heated at +/−30° C. within the meltingtemperature of (b) the ethylene-based polymer. The solid carriercomponent may be disposed in a second or later zone of the extruder,which may be heated at 10° C. to 90° C. above the melting temperature of(b) the ethylene-based polymer. As noted above, the temperature utilizedis typically less than a degradation temperature of the startingmaterials of the WPC composition. Alternatively, the die of the extrudermay also be heated, and the temperatures utilized by the extruder,including the temperature of any zone and the die, may be selected suchthat the temperatures do not exceed a degradation temperature of (a) thelignocellulosic-based filler. The degradation temperature of (a) thelignocellulosic-based filler is contingent on the selection thereof, asunderstood by one of skill in the art.

The method described above may be used to produce various WPC articles,such as WPC building materials. Such WPC building materials includeresidential and/or commercial building and construction products andapplications, e.g. decking, railing, siding, fencing, window framing,flooring, trim, and skirts.

EXAMPLES

These examples are intended to illustrate the invention to one skilledin the art and are not to be interpreted as limiting the scope of theinvention set forth in the claims. The starting materials in Tables 3-5were used in these examples.

TABLE 3 Ethylene - Based Polymers Used Herein Melting Temper- StartingDensity I₂ ature Material Type (g/cm³) (g/10 min) (° C.) HDPE 1 highdensity polyethylene 0.950 12 132 HDPE 2 narrow molecular weight 0.9526.8 131 distribution high density polyethylene homopolymer HDPE 3 highdensity polyethylene 0.952 4.4 131 HDPE 4 high density polyethylene0.961 0.80 133 homopolymer HDPE 5 high density polyethylene 0.954 20 130HDPE 6 high density polyethylene 0.952 10 130 HDPE 7 high densitypolyethylene 0.965 8.3 133 LLDPE 1 ethylene/1-octene linear- 0.917 2.3123 low-density polyethylene copolymer LLDPE 2 ethylene/1-octene linear-0.919 6.0 124 low-density polyethylene copolymer

The ethylene-based polymers in Table 3 are each commercially availablefrom The Dow Chemical Company of Midland, Mich., USA. In Table 2,densities were measured by ASTM D792—13; melt indexes were measured byASTM D1238—13 at 190° C. and 2.16 Kg; and melting temperatures weremeasured by DSC.

TABLE 4 Maleated Ethylene-Based Polymers Starting Material B-1 B-2 Typea random ethylene high density copolymer incorporating polyethylene amonomer which is grafted with very classified as being high maleic amaleic anhydride anhydride copolymer equivalent graft level Density(g/cm³) 0.940 0.962 I₂ (g/10 min) 25 2.0 Melting Temperature 108 130 (°C.)

The maleated ethylene-based polymers are both commercially availablefrom The Dow Chemical Company of Midland, Mich., USA. In Table 4,densities were measured by ASTM D792—13; melt indexes were measured byASTM D1238—13 at 190° C. and 2.16 Kg; and melting temperatures weremeasured by DSC. Melting temperature of B-1 was measured according toASTM D3418—15, and melting temperature of B-2 was measured by DSCwherein a film was conditioned at 230° C. for 3 minutes before coolingat a rate of 10° C. per minute to a temperature of −40° C. After thefilm was kept at −40° C. for 3 minutes, the film was heated to 200° C.at a rate of 10° C. per minute.

TABLE 5 Siloxanes Starting Material Description C-1bis-hydroxyl-terminated polydimethylsiloxane with viscosity of 12,000mPa · s to 15,000 mPa · s C-2 bis-hydroxyl-terminatedpolydimethylsiloxane with viscosity of 5,400 mPa · s to 6,600 mPa · sC-3 bis-hydroxyl-terminated polydimethylsiloxane with viscosity of16,500 mPa · s C-4 bis-hydroxyl-terminated polydimethylsiloxane withviscosity of 20,000 mPa · s

In Table 5, the bis-hydroxyl-terminated polydimethylsiloxanes werecommercially available from Dow Silicones Corporation of Midland, Mich.,USA. The viscosities of the bis-hydroxyl-terminatedpolydimethylsiloxanes were measured at 25° C. at 5 RPM on a BrookfieldDV-III cone & plate viscometer with #CP-52 spindle.

In this Reference Example 1, a solid carrier component in pellet formwas produced using a 26 mm twin screw extruder. Starting material (A)the ethylene-based polymer and starting material (B) the maleatedethylene-based polymer were fed in via the feed throat in the firstbarrel section. When used, starting material (D) the filler (talc, whichwas untreated and had an average particle size of 1.9 μm) was also fedin via the feed throat in the first barrel section. Starting material(C) the polydiorganosiloxane was injected into the fourth of elevenbarrel sections onto a screw section with mixing. The resultingcomposition was pelletized using a Gala underwater pelletizer forconsistency and collected for testing. All samples were cooled to roomtemperature and aged a minimum of 48 hours before any testing.

In this Reference Example 2, a solid carrier component in pellet formwas produced using a 25 mm twin screw extruder. Starting material (A)the ethylene-based polymer and starting material (B) the maleatedethylene-based polymer were fed in via the feed throat in the firstbarrel section. When used, starting material (D) the filler: CaCO₃(Calcium carbonate which was untreated and had an average particle sizeof 3 μm) was also fed in via the feed throat in the first barrelsection. Starting material (C) the polydiorganosiloxane was injectedinto the fourth of twelve barrel sections onto a screw section withmixing. The resulting composition was cooled via full immersion in waterbath and pelletized using a strand pelletizer. In this Reference Example2, bleed of the bis-hydroxyl-terminated polydiorganosiloxane from thepellets prepared in Reference Example 1 and Reference Example 2 wasevaluated, as follows. Each sample (4 g) was placed into pre-weighedaluminum pans lined with Whatman™ #1 filter paper (5.5 cm diameter) suchthat the surface of the aluminum pan was covered fully by the filterpaper, but the filter paper was not bent. The pellets were evenly spreadout across the filter paper in a semi-uniform layer. The samples wereleft standing at room temperature on the bench or at the saidtemperature in a convection oven for the Aging Time. After aging, thepellets were left to stand at room temperature for at least 4 hours, andthe pellets were placed in a 20 mL scintillation vial. The filter paperwas weighed to determine aged filter paper weight. Bleed was determinedaccording to the formula below:

${{Bleed}\mspace{14mu}(\%)} = {100 \times \frac{\begin{matrix}{{{Aged}\mspace{14mu}{Filter}\mspace{14mu}{Paper}\mspace{14mu}{Weight}} -} \\{{Starting}\mspace{14mu}{Filter}\mspace{14mu}{Paper}\mspace{14mu}{Weight}}\end{matrix}}{\begin{matrix}{{Total}\mspace{14mu}{Pellet}\mspace{14mu}{Weight} \times} \\{{Fraction}\mspace{14mu}{Siloxane}\mspace{14mu}{in}\mspace{14mu}{Pellet}}\end{matrix}}}$

The starting materials and their amounts are shown below in Tables 6 and7. Aging conditions and siloxane bleed are also reported below in Tables6 and 7.

TABLE 6 Aging Siloxane PE MAPE Siloxane Talc T Aging Time bleed ExamplePE (%) MAPE (%) Siloxane (%) (%) (° C.) (weeks) (%) Comparative 1 HDPE 460 B-2 20 C-1 20 0 70 4 8.8 Comparative 2 HDPE 1 50 B-2 25 C-1 25 0 70 41.5 Comparative 3 HDPE 3 40 B-2 25 C-1 25 10 70 4 3.3 Comparative 4 HDPE2 40 B-2 25 C-1 25 10 70 4 2.7 Comparative 5 HDPE 2 40 B-2 25 C-2 25 1070 4 9 Comparative 6 HDPE 3 40 B-2 25 C-1 25 10 23 3 1.1 Comparative 7HDPE 2 40 B-2 25 C-1 25 10 23 3 0.8 Comparative 8 HDPE 2 40 B-2 25 C-225 10 23 3 5.8 Working 9 LLDPE 1 60 B-2 20 C-1 20 0 70 4 0.2 Working 10HDPE 1 70 B-2 15 C-1 15 0 70 4 0.3 Working 11 HDPE 2 70 B-2 15 C-1 15 070 4 0.1 Working 12 HDPE 2 60 B-2 20 C-1 20 0 70 4 0.2 Working 13 LLDPE2 70 B-2 15 C-1 15 0 70 4 0.2 Working 14 HDPE 2 60 B-2 20 C-1 20 0 70 40.2 Working 15 HDPE 2 80 B-2 10 C-1 10 0 70 4 0.3 Working 16 LLDPE 2 60B-2 20 C-1 20 0 70 4 0.1 Working 17 HDPE 2 60 B-2 20 C-2 20 0 70 4 0.2Working 18 LLDPE 2 60 B-2 20 C-2 20 0 70 4 0.1 Working 19 LLDPE 2 60 B-220 C-1 20 0 70 4 0.2 Working 20 HDPE 1 60 B-2 20 C-1 20 0 70 4 0.2Working 21 HDPE 1 80 B-2 10 C-1 10 0 70 4 0.3 Working 22 LLDPE 2 80 B-210 C-1 10 0 70 4 0.2 Working 23 HDPE 3 60 B-2 20 C-1 20 0 70 3 0.6Working 24 HDPE 3 50 B-2 20 C-1 20 10 70 3 0.9 Working 25 HDPE 2 50 B-220 C-1 20 10 70 3 0.7 Working 26 HDPE 2 60 B-1 20 C-1 20 0 70 3 0.4Working 27 HDPE 3 60 B-2 20 C-2 20 0 70 3 0.5 Working 28 HDPE 2 60 B-120 C-2 20 0 70 3 0.8 Working 29 HDPE 2 60 B-2 20 C-2 20 0 70 3 0.6Working 30 HDPE 2 60 B-2 20 C-1 20 0 70 3 0.1 Working 31 HDPE 3 60 B-220 C-1 20 0 23 3 0.2 Working 32 HDPE 3 50 B-2 20 C-1 20 10 23 3 0.4Working 33 HDPE 2 50 B-2 20 C-1 20 10 23 3 0.3 Working 34 HDPE 2 60 B-120 C-1 20 0 23 3 0.3 Working 35 HDPE 3 60 B-2 20 C-2 20 0 23 3 0.1Working 36 HDPE 2 60 B-1 20 C-2 20 0 23 3 0.3 Working 37 HDPE 2 60 B-220 C-2 20 0 23 3 0.2 Working 38 HDPE 2 60 B-2 20 C-1 20 0 23 3 0.1Working 39 HDPE 7 55 B-2 20 C-4 25 0 70 2 0.01 Working 40 HDPE 3 50 B-225 C-3 25 0 70 2 0.1 Working 41 LLDPE 2 70 B-2 20 C-2 10 0 70 2 Non-detecable

TABLE 7 Aging Siloxane PE MAPE Siloxane CaCO3 T Aging time bleed ExamplePE (%) MAPE (%) Siloxane (%) (%) (° C.) (weeks) (%) Working 42 HDPE 3 40B-2 25 C-3 25 10 70 2 0.79 Note: Comparative examples 1 to 8 and Workingexamples 9 to 38 were made by the method of Reference Example 1. Workingexamples 39-42 were made by the method of Reference Example 2.

INDUSTRIAL APPLICABILITY

The EXAMPLES above show that a solid carrier component with low bleed ofthe bis-hydroxyl-terminated polydiorganosiloxane could be prepared. “Lowbleed” means that bis-hydroxyl-terminated polydiorganosiloxane migratingout of the solid carrier component is <0.5% after aging at 23° C. for upto 3 weeks and/or <1% after aging at 70° C. for at least 3 weeks, asmeasured by the test method in Reference Example 2. Alternatively, “Lowbleed” may also refer to an amount of bis-hydroxyl-terminatedpolydiorganosiloxane migrating out of the solid carrier component thatis <0.8% after aging at 70° C. for at least 2 weeks.

Working Examples 9-38 showed that a low bleed solid carrier componentcould be prepared using 40 weight % to 80 weight % of (A) anethylene-based polymer as described above, 10 weight % to <25 weight %of (B) a maleated ethylene-based polymer as described above, 10 weight %to <25 weight % of (C) a bis-hydroxyl-terminated polydiorganosiloxane asdescribed above; and 0 to 10 weight % of (D) a filler as describedabove.

Comparative Example 1 showed that using an ethylene-based polymer with amelt index <2 g/10 min failed to produce a solid carrier component withbleed <1% after aging at 70° C. for 4 weeks, however, Working Examples9, 12, 14, 16, 19, and 20 showed that with the same types and amounts ofeach of the maleated ethylene-based polymer and thebis-hydroxyl-terminated polydiorganosiloxane, a solid carrier componentwith bleed <1% after aging at 70° C. for 4 weeks could be produced usingdifferent ethylene-based polymers with melt indexes 2.3 g/10 min.Comparative Examples 2-8 showed that using amounts 25% of each of amaleated ethylene-based polymer and a bis-hydroxyl-terminatedpolydiorganosiloxane produced solid carrier components that did not havelow bleed under the conditions tested in Reference Example 2.

Definitions and Usage of Terms

Unless otherwise indicated by the context of the specification: allamounts, ratios, and percentages herein are by weight; the articles ‘a’,‘an’, and ‘the’ each refer to one or more; and the singular includes theplural. The SUMMARY and ABSTRACT are hereby incorporated by reference.The transitional phrases “comprising”, “consisting essentially of”, and“consisting of” are used as described in the Manual of Patent ExaminingProcedure Ninth Edition, Revision 08.2017, Last Revised January 2018 atsection § 2111.03 I., II., and III. The use of “for example,” “e.g.,”“such as,” and “including” to list illustrative examples does not limitto only the listed examples. Thus, “for example” or “such as” means “forexample, but not limited to” or “such as, but not limited to” andencompasses other similar or equivalent examples. The abbreviations usedherein have the definitions in Table 8.

TABLE 8 Abbreviations Abbreviation Definition ° C. degrees Celsius cmcentimeters cSt centistokes DSC differential scanning calorimetry ggrams GPC gel permeation chromatography HDPE high-density polyethyleneKg kilograms LLDPE linear-low-density polyethylene MAPE maleatedethylene-based polymer MDPE medium-density polyethylene mg milligramsmin minutes mL milliliters mm millimeters mPa · s milliPascal · secondsMWD molecular weight distribution N normal PDI polydispersity index PEethylene-based polymer PTFE polytetrafluoroethylene μL microliters ULDPEultra low density polyethylene, which has a density of 0.880 to 0.912g/cm3, and which may be prepared with Ziegler-Natta catalysts, chromecatalysts, or single-site catalysts including, but not limited to,bis-metallocene catalysts and constrained geometry catalysts μmmicrometers WPC wood plastic composite

The following test methods were used to measure properties of thestarting materials herein.

Melt indices of ethylene-based polymers and maleated ethylene-basedpolymers, abbreviated I₂ or I2, were measured in accordance to ASTMD1238—13 at 190° C. and at 2.16 Kg. Their values are reported in g/10min.

Samples of ethylene-based polymers and maleated ethylene-based polymerswere prepared for density measurement according to ASTM D4703.Measurements were made, according to ASTM D792—13, Method B, within onehour of sample pressing.

Peak melting point (Melting Temperature) of ethylene-based polymers andmaleated ethylene-based polymers was determined by DSC, where a film wasconditioned at 230° C. for 3 minutes before cooling at a rate of 10° C.per minute to a temperature of −40° C. After the film was kept at −40°C. for 3 minutes, the film was heated to 200° C. at a rate of 10° C. perminute.

“MWD” is defined as the ratio of weight average molecular weight tonumber average molecular weight (M_(w)/M_(n)). M_(w) and M_(n) aredetermined according to conventional GPC methods.

Viscosities of polydiorganosiloxanes were measured at 25° C. at 5 RPM ona Brookfield DV-III cone & plate viscometer with #CP-52 spindle.

The invention has been described in an illustrative manner, and it is tobe understood that the terminology which has been used is intended to bein the nature of words of description rather than of limitation. Withrespect to any Markush groups relied upon herein for describingparticular features or aspects, different, special, and/or unexpectedresults may be obtained from each member of the respective Markush groupindependent from all other Markush members. Each member of a Markushgroup may be relied upon individually and or in combination and providesadequate support for specific embodiments within the scope of theappended claims.

Furthermore, any ranges and subranges relied upon in describing thepresent invention independently and collectively fall within the scopeof the appended claims, and are understood to describe and contemplateall ranges including whole and/or fractional values therein, even ifsuch values are not expressly written herein. One of skill in the artreadily recognizes that the enumerated ranges and subranges sufficientlydescribe and enable various embodiments of the present invention, andsuch ranges and subranges may be further delineated into relevanthalves, thirds, quarters, fifths, and so on. As just one example, arange of “1 to 18” may be further delineated into a lower third, i.e., 1to 6, a middle third, i.e., 7 to 12, and an upper third, i.e., from 13to 18, which individually and collectively are within the scope of theappended claims, and may be relied upon individually and/or collectivelyand provide adequate support for specific embodiments within the scopeof the appended claims. In addition, with respect to the language whichdefines or modifies a range, such as “at least,” “greater than,” “lessthan,” “no more than,” and the like, it is to be understood that suchlanguage includes subranges and/or an upper or lower limit.

Embodiments of the Invention

In a first embodiment, a solid carrier component for use in preparing aWPC article comprises:

40 weight % to 80 weight % of (A) an ethylene-based polymer with a meltindex>2 g/10 min measured according to ASTM D1238—13 at 190° C. and 2.16Kg,10 weight % to <25 weight % of (B) a maleated ethylene-based polymer,10 weight % to <25 weight % of (C) a bis-hydroxyl-terminatedpolydialkylsiloxane of formula

where each R is an independently selected alkyl group of 1 to 18 carbonatoms, and subscript x has a value sufficient to give thepolydialkylsiloxane a viscosity of 5,000 mPa·s to 25,000 mPa·s measuredat 25° C. at 5 RPM on a Brookfield DV-III cone & plate viscometer with#CP-52 spindle; and 0 to 10 weight % of (D) a filler,where each weight % is based on combined weights of all startingmaterials in the solid carrier component.

In a second embodiment, in the solid carrier component of the firstembodiment, the melt index of the high density polyethylene is 2.3 g/10min to 20 g/10 min, and starting material (A) is present at 50 weight %to 70 weight %.

In a third embodiment, in the solid carrier component of the firstembodiment or the second embodiment, the melt index of the high densitypolyethylene is 4.4 g/10 min to 20 g/10 min.

In a fourth embodiment, in the solid carrier component of any one of thepreceding embodiments, starting material (B), the maleatedethylene-based polymer, has a melt index of 2 g/10 min to 25 g/10 minmeasured according to ASTM D1238—13 at 190° C. and 2.16 Kg and a maleicanhydride content of 0.25 weight % to 2.5 weight %, and startingmaterial (B) is present at 10 weight % to 20 weight %.

In a fifth embodiment, in any one of the preceding embodiments, in theformula for starting material (C), the bis-hydroxyl terminatedpolydialkylsiloxane, each R is an independently selected alkyl group of1 to 12 carbon atoms, and subscript x has a value sufficient to give thepolydialkylsiloxane the viscosity of 5,000 mPa·s to 15,000 mPa·s.

In a sixth embodiment, in the solid carrier component of the fourthembodiment, each R is a methyl group, and (C) the polydialkylsiloxane ispresent at 10 weight % to 20 weight %.

In a seventh embodiment, in the solid carrier component of any one ofthe preceding embodiments, starting material (D) is present in anamount >0 to 10 weight %, and starting material (D) comprises talc.

In an eighth embodiment, the solid carrier component of any one of thefirst to sixth embodiments is free of starting material (D), the filler.

In a ninth embodiment, the solid carrier component of any one of thefirst to seventh embodiments, the solid carrier component consistsessentially of starting materials (A), (B), (C), and (D).

In a tenth embodiment, in any one of the first embodiment to the sixthembodiment or the eighth embodiment, the solid carrier componentconsists essentially of starting materials (A), (B), and (C).

In an eleventh embodiment, the solid carrier component of the tenthembodiment consists of starting materials (A), (B), and (C).

In a twelfth embodiment, a method for preparing a composition for a woodplastic composite article comprises combining:

a sufficient amount of (i) the solid carrier component of any one of thepreceding embodiments give the composition a content of the bis-hydroxylterminated polydiorganosiloxane of 0.5 weight % to 4 weight %;

10 weight % to 80 weight % based on total weight of the composition of(ii) an ethylene-based polymer, which may be the same as or differentfrom the high density polyethylene for starting material (A) in thesolid carrier component; and

10 weight % to 89.5 weight % based on total weight of the composition of(iii) a lignocellulosic-based filler.

In a thirteenth embodiment, in the method of the twelfth embodiment, thelignocellulosic-based filler comprises a lignocellulosic materialderived from wood, plants, agricultural by-products, chaff, sisal,bagasse, wheat straw, kapok, ramie, henequen, corn fiber or coir, nutshells, flax, jute, hemp, kenaf, rice hulls, abaca, peanut hull, bamboo,straw, lignin, starch, or cellulose and cellulose-containing products,and combinations thereof.

In a fourteenth embodiment, in the method of the twelfth embodiment orthe thirteenth embodiment, the lignocellulosic-based filler is a woodfiller comprising lignin in an amount of 18 weight % to 35 weight % andcarbohydrate in an amount of 65 weight % to 75 weight %, and optionallyinorganic minerals in an amount up to 10 weight %.

In a fifteenth embodiment, in the method of any one of the twelfth tothe fourteenth embodiments, the lignocellulosic-based filler is a woodfiller comprising 29 weight % to 57 weight % alpha-cellulose.

In an sixteenth embodiment, in the method of any one of the twelfth tothe fifteenth embodiments, (ii) the ethylene-based polymer is apolyethylene selected from the group consisting of High DensityPolyethylene (HDPE), Medium Density Polyethylene (MDPE), Low DensityPolyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), LowDensity Low Molecular Weight Polyethylene (LDLMWPE), and a combinationthereof.

In a seventeenth embodiment, in the method of any one of the twelfth tothe sixteenth embodiments, the ethylene-based polymer is selected fromthe group consisting of HDPE, LLDPE, and a combination thereof.

In an eighteenth embodiment, in the method of any one of the twelfth tothe seventeenth embodiments, the ethylene-based polymer comprises 50%recycled polyethylene

In a nineteenth embodiment, the method of any one of the twelfth to theeighteenth embodiments further comprises forming a wood plasticcomposite article from the composition.

In a twentieth embodiment, in the method of the nineteenth embodiment,the composition further comprises an additional starting materialselected from the group consisting of (e) an additional filler which isdistinct from the lignocellulosic-based filler of starting material (a),(f) a colorant, (g) a blowing agent, (h) a UV stabilizer, (i) anantioxidant, (j) a process aid, (k) a preservative, (l) a biocide, (m) aflame retardant, (n) an impact modifier, and (o) a combination of two ormore thereof.

In a twenty-first embodiment, in the method of the nineteenth embodimentor the twentieth embodiment, the wood plastic composite article isselected from the group consisting of decking, railing, fencing, siding,flooring, trim, skirts, and window framing.

In a twenty-second embodiment, in the method of the twenty-firstembodiment, the wood plastic composite article is decking.

In a twenty-third embodiment, the method of the twenty-second embodimentfurther comprises: adding a cap stock layer to the decking afterforming.

1. A solid carrier component comprising: 40 weight % to 80 weight % of(A) an ethylene-based polymer with a melt index>2 g/10 min measuredaccording to ASTM D1238—13 at 190° C. and 2.16 Kg, 10 weight % to <25weight % of (B) a maleated ethylene-based polymer, 10 weight % to <25weight % of (C) a bis-hydroxyl terminated polydiorganosiloxane with aviscosity of 5,000 mPa·s to 25,000 mPa·s measured at 25° C. at 5 RPM ona Brookfield DY-III cone & plate viscometer with #CP-52 spindle; and 0to 10 weight % of (D) a filler, where each weight % is based on combinedweights of all starting materials in the solid carrier component.
 2. Thesolid carrier component of claim 1, where for starting material (A) themelt index is 2.3 g/10 min to 12 g/10 min, the density is 0.917 g/cm³ to0.952 g/cm³ measured according to ASTM D792—13 and starting material (A)is present at 50 weight % to 70 weight %.
 3. The solid carrier componentof claim 1, where starting material (A) is selected from the groupconsisting of an ethylene homopolymer and an ethylene/1-octenecopolymer.
 4. The solid carrier component of claim 1, where startingmaterial (B) has a melt index of 0.1 g/10 min to 25 g/10 min and amaleic anhydride content of 0.25 weight % to 2.5 weight %, and startingmaterial (B) is present at 10 weight % to 20 weight %.
 5. The solidcarrier component of claim 1, where starting material (C) is abis-hydroxyl-terminated polydialkylsiloxane of formula

where each R is an independently selected alkyl group of 1 to 12 carbonatoms, and subscript x has a value sufficient to give thepolydialkylsiloxane the viscosity of 5,000 mPa·s to 15,000 mPa·s.
 6. Thesolid carrier component of claim 5, where each R is a methyl group, andstarting material (C) is present at 10 weight % to 20 weight %.
 7. Thesolid carrier component of claim 1, where starting material (D) ispresent in an amount >0 to 10 weight %, and starting material (D)comprises talc.
 8. The solid carrier component of claim 1, where thesolid carrier component is free of starting material (D), the filler. 9.The solid carrier component of claim 1, where combined weights ofstarting materials (A), (B), (C), and (D) total 100 weight % of thesolid carrier component.
 10. A method for preparing a composition for awood plastic composite article comprising a sufficient amount of (i) asolid carrier component to give the composition a content of thebis-hydroxyl terminated polydiorganosiloxane of 0.5 weight % to 4 weight%; 10 weight % to 80 weight % based on total weight of the compositionof (ii) an ethylene-based polymer, which may be the same as or differentfrom the ethylene-based polymer for starting material (A) in the solidcarrier component; and 10 weight % to 89.5 weight % based on totalweight of the composition of (iii) a lignocellulosic-based filler; wherethe solid carrier component comprises 40 weight % to 80 weight % of (A)an ethylene-based polymer with a melt index>2 g/10 min measuredaccording to ASTM D1238—13 at 190° C. and 2.16 Kg, 10 weight % to <25weight % of (B) a maleated ethylene-based polymer, 10 weight % to <25weight % of (C) a bis-hydroxyl terminated polydiorganosiloxane with aviscosity of 5,000 mPa·s to 25,000 mPa·s measured at 25° C. at 5 RPM ona Brookfield cone & plate viscometer with #CP-52 spindle; and 0 to 10weight % of (D) a filler,  where each weight % in the solid carriercomponent is based on combined weights of all starting materials in thesolid carrier component.
 11. The method of claim 10, where (iii) thelignocellulosic-based filler comprises a lignocellulosic materialderived from wood, plants, agricultural by-products, chaff, sisal,bagasse, wheat straw, kapok, ramie, henequen, corn fiber or coir, nutshells, flax, jute, hemp, kenaf, rice hulls, abaca, peanut hull, bamboo,straw, lignin, starch, or cellulose and cellulose-containing products,and combinations thereof.
 12. The method of claim 10, where (ii) theethylene-based polymer is a polyethylene selected from the groupconsisting of High Density Polyethylene, Medium Density Polyethylene,Low Density Polyethylene, Linear Low Density Polyethylene, Low DensityLow Molecular Weight Polyethylene, and a combination thereof.
 13. Themethod of claim 12, where (ii) the ethylene-based polymer comprises ≥50%recycled polyethylene.
 14. The method of claim 10, further comprisinguse of the composition to fabricate the wood plastic composite article.15. The method of claim 14, where the wood plastic composite article isa building material selected from the group consisting of decking,railing, fencing, siding, trim, skirts, window framing, and flooring.16. A solid carrier component comprising: 40 weight % to 80 weight % of(A) an ethylene-based polymer with a melt index>2 g/10 min measuredaccording to ASTM D1238—13 at 190° C. and 2.16 Kg, 10 weight % to 25weight % of (B) a maleated ethylene-based polymer, 10 weight % to 25weight % of (C) a bis-hydroxyl terminated polydiorganosiloxane with aviscosity of 5,000 mPa·s to 25,000 mPa·s measured at 25° C. at 5 RPM ona Brookfield DY-III cone & plate viscometer with #CP-52 spindle; and 0to 10 weight % of (D) a filler, where each weight % is based on combinedweights of all starting materials in the solid carrier component.